CN102725385B

CN102725385B - Stabilized blends containing friction modifiers

Info

Publication number: CN102725385B
Application number: CN201080062546.XA
Authority: CN
Inventors: J·J·穆莱; J·D·伯林顿; E·E·德尔布里奇
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 2009-11-30
Filing date: 2010-11-17
Publication date: 2015-05-27
Anticipated expiration: 2030-11-17
Also published as: WO2011066141A2; US20120283158A1; EP2507349B1; WO2011066141A3; CN102725385A; CA2782542A1; BR112012012893A2; US20170058230A1; US9528067B2; EP2507349A2

Abstract

The present invention relates to functional fluid compositions containing friction modifiers, and specifically stable compositions containing friction modifiers with limited solubility in and/or limited compatibility with the functional fluids with which they are used. In particular the present invention deals with functional fluids used in internal combustion engines, such as engine oils, and friction modifiers that contain one or more amide functional groups, where the friction modifier is present in the functional fluid composition at levels that would otherwise cause the composition to be unstable and/or hazy.

Description

Stabilized mixture containing friction improver

Background of invention

The present invention relates to the functional fluid composition containing friction improver, especially contain the stable composition of the friction improver in the functional liquid used together with them with limited solubility and/or limited compatibility.

Friction improver is known with them to the importance of all kinds of functional liquid.But many friction improvers are owing to only can use with restricted manner for the solvability of functional liquid wherein and/or compatibility problem with them.Many friction improvers, especially have limited solubility derived from those of hydroxycarboxylic acid in functional liquid is as engine oil and gear oil.Can pass by time when these friction improvers use with level more than its solvability and/or the consistency limit and spill from functional fluid composition and/or cause composition to show preformed casse or muddiness.

These are the serious problems in fluid production and blending means and field.Such as, functional liquid additive manufacturer can sell the homogeneous phase additive-package of performance chemicals, then can be added to obtain final lubricant in base oil, final lubricant sells finally be delivered in equipment to be lubricated by lubricant again in storage tank, bucket, tank and plastic containers.For keeping the performance guarantee of final lubricant or other functional liquid any in its equipment of use, enriched material and lubricant must keep homogeneous phase in those steps.In other words, in the various materials that the additive of all existence must contact with it, each is compatible, and/or to final fluid, finds itself from additive-package to enriched material.This strict standard greatly limit many additives, comprises the selection of friction improver described herein and effective processing horizontal.These friction improvers can be supplied to the performance that functional liquid improves, but do not widely use, and/or do not use, because additive can not meet above-mentioned solvability and/or compatibility requirements with optimum level.

In the art, pass by time and the functional fluid composition that spills one or more components can not suitably perform, unless they mixed well before use, or by removing with the strainer of the device-dependent using functional liquid.The preformed casse of functional liquid and/or muddiness, can be used as the turbidimetry of fluid, is usually considered as the signal of composition instability, can be maybe the initial stage be separated and/or component spills.This situation is undesirable due to performance and aesthstic related causes in functional fluid composition.This feasibility creates the constraint condition of the use to various friction improver, such as effective maximum processing rate.

Not about these solvabilities and/or the consistency restriction of the use of these friction improvers; larger performance and equipment protection may be realized, comprise the equipment part of such as lubricant or lubrication as the prolongs life of engine, automatic transmission, wheel gearing etc.Also fuel economy and the viscosity stability of improvement can be realized.Depend on more effective, but when carrying in a usual manner, the selection of chemical unstable viewed from consistency or stability viewpoint, larger performance even can realize with less amount and more substantial chemical.

Need the friction improver containing more a large amount, still keep stable and/or limpid functional fluid composition simultaneously.Particularly need as mentioned above with otherwise composition level that is unstable and/or preformed casse can be caused to comprise functional fluid composition derived from the friction improver of hydroxycarboxylic acid as engine oil composition.The present composition and method overcome these constraint conditions and therefore allow with otherwise impossible, simultaneously still keep the stability of functional fluid composition and/or the level of the transparency to use these friction improvers.

Summary of the invention

Find the friction improver that can contain a large amount, particularly there is the functional fluid composition of the friction improver of limited solubility and/or consistency in they are for functional fluid composition wherein, thus allow that this friction improver of more a large amount is in these functional fluid compositions, keeps the stability of total composition, the transparency and/or consistency simultaneously.

The invention provides the composition comprising following component: (a) can comprise solvent, functional liquid or its medium combined; (b) friction modifier component in medium is not exclusively dissolved in; (c) to dissolve in (a) and to improve with (b) solvability making (b) in (a) that interacts, or may the stable component of improvement compared with (b) solvability in (a) combination with (b) and (b) solvability in (a) more accurately.The form that component (b) and (c) can be less than the discrete particles of 10 μm with mean diameter is present in component (a).

In some embodiments, component (b) friction improver comprises the compound containing one or more amide functional group, and component (c) is stablized component and is comprised: (i) metal: matrix, than the high alkaline detergent being greater than 3:1, comprises boration variant; (ii) alkyl imidazoline; (iii) amine salt of hydrocarbyl phosphate or acid esters, hydrocarbylthio phosphoric acid or acid esters, hydrocarbyl dithiophosphoric acid or acid esters, one or more these acid and acid esters, or its combination; (iv) alkylbenzene sulfonate or derivatives thereof; Or its combination.

In some embodiments, the present composition causes the improvement of composition turbidity compared with the same combination not stablize component containing (c), as pass through lower jackson turbidity unit (JTU) and/or than turbid turbidity unit (NTU) value define.In some embodiments, maximum JTU and/or the NTU value of the present composition is 100.

The present invention also provides preparation the limpid and method of stable composition as described herein, and described method comprises the steps: that component (b) and (c) add in component (a) by (I); (II) particle of component (b) and (c) is made to have the mean diameter being less than 10 μm described component mixing.

Detailed Description Of The Invention

Set forth below by indefiniteness and describe each preferred feature and embodiment.

The invention provides and allow otherwise can not use and/or use some friction improver in functional fluid composition that the level that can not allow with the present invention uses and do not produce instability, the composition of unlimpid and/or preformed casse composition and method.

The type that the present composition and method can be used for the functional liquid wherein and therewith used can comprise: gear oil, gear compound, hydraulic fluid, engine oil, two-stroke cycle oil, metal working fluids, fuel etc.In one embodiment, functional liquid is engine oil.In another embodiment, functional liquid is gear oil.In another embodiment, functional liquid is power transmitting fluids.In another embodiment, functional liquid is hydraulic fluid.In another embodiment, functional liquid is fuel.

In some embodiments, the present invention does not comprise e Foerderanlage as holding friction improver and making it and it add the use of the device that functional liquid wherein contacts.In some embodiments, the present invention does not comprise the use of gelatinous composition or solids composition, and wherein these one or more components of based composition slow releasing are in functional liquid.But the invention provides the method be incorporated to by friction improver for the use by combination of components in functional liquid, this generation has high friction improver content, simultaneously still for stable, limpid and/or without the functional liquid of preformed casse.

In some embodiments, the invention provides the composition of more stable than composition identical except lacking one or more components, limpider and/or less preformed casse.In some embodiments, the component lacked is for stablize component.In other embodiments, the present composition has turbidity lower compared with composition identical except lacking the present invention and stablizing component.In some these embodiments, the turbidity of composition is expressed as JTU and/or NTU value.In other embodiments, the present composition has maximum JTU and/or the NTU value of 100,90 or even 80.

JTU and NTU value can be measured by US EPA method 180.1.JTU and NTU value also can not further dilutedly by using Monitek Model 151 turbidometer to measure with jackson turbidity unit (JTU).

medium

The present composition comprises medium.Medium can be solvent, functional liquid, multifunctional additive for lubricating oils or its combination.

Suitable solvent comprise aliphatic hydrocrbon, aromatic hydrocarbon, containing oxygen composition or its mixture.Alcohol, ketone, the ester of carboxylic acid, glycol and/or polyoxyethylene glycol can be comprised containing oxygen composition, or its mixture.Suitable solvent also comprise there is lubricant viscosity oil, petroleum naphtha, toluene, dimethylbenzene or its combination.The oil with lubricant viscosity can comprise natural oil, synthetic oil or its mixture.The oil with lubricant viscosity can organize II, III, IV, V base oil or its mixture for API (American Petroleum Institute).Have except the oil of lubricant viscosity except comprising, the example of commercially available aliphatic hydrocarbon solvent or thinner is the Pilot that can be obtained by PetrochemCarless ^tM140 and Pilot ^tM299 and Pilot ^tM900, Petro-Canada ^tM100N, Nexbase ^tM, Yubase ^tMwith 4-6cSt poly-(alpha-olefin).

Suitable functional liquid comprises any above-listed functional liquid, comprises the mixture of this kind of fluid.In many embodiments, except the component (b) hereafter described in detail and (c), functional liquid or other material as medium contain other additive.These other additives are described in greater detail in hereinafter.

In one embodiment of the invention, medium and/or total composition substantially not containing or not containing be selected from sulphur, phosphorus, vitriol ash and combination at least a member, in other embodiments, fuel composition contains and is less than 20ppm, is less than 15ppm, is less than 10ppm, or is less than at least a member being selected from sulphur, phosphorus, vitriol ash and combining of 1ppm.

In one embodiment, medium and stable component can be identical material.Namely a kind of material can perform the function of two kinds of components.Such as when the present invention is the form of enriched material, existing medium can serve as stable component, and vice versa.Then can this enriched material be added in functional liquid as top process and/or additive-package, produce stable and uniform functional liquid, described functional liquid otherwise stabilizer component/dielectric material not in the presence of can be muddy or incompatible.

friction improver

The present composition comprises friction modifier component.Friction modifier component can comprise at least one and be ready to use in friction improver not exclusively solvable and/or compatible in medium wherein and/or functional liquid at it.The not exclusively solvable and/or compatible friction improver that means can not keep dissolving and/or be suspended in the fluid that it adds wherein, causes fluid to show preformed casse and/or muddiness, or its any combination.In some embodiments, friction improver causes it to have NTU and/or the JTU value of 80,90 or even more than 100 for fluid wherein.In some embodiments, this fluid is that functional fluid composition is as final lubricant or multifunctional additive for lubricating oils.

In some embodiments, friction improver of the present invention can dissolve with lower concentration and fluid and/or compatible, but becomes less solvable and/or compatible at higher concentrations.In some embodiments, be applicable to friction improver in the present invention with or more than 0.1,0.15,0.2,0.3,0.5 or 1.0 % by weight concentration be present in fluid time not exclusively solvable and/or compatible as defined above.

In some embodiments, friction improver of the present invention comprises the compound containing one or more amide functional group.Suitable friction improver comprises the compound that formula (I) represents

formula I

Wherein X ⁴for Sauerstoffatom or sulphur atom; And each R ²and R ³be hydrogen or alkyl independently.The example of suitable frictional improving agent comprises oleylamide, stearylamide or its combination.

Fatty amide has been described in detail in U.S. Patent No. 4, and 280, in 916.Suitable acid amides is C ₈-C ₂₄aliphatic monocarboxylic amides and be known.Fatty acid base compound and ammonia or amine react and produce fatty amide.Lipid acid and the acid amides derived by it can be saturated or undersaturated.Important lipid acid comprises lauric acid (C ₁₂), palmitinic acid (C ₁₆) and stearic acid (C ₁₈).Other important unsaturated fatty acids comprises oleic acid, linoleic acid plus linolenic acid, and they are all is C ₁₈.In one embodiment, fatty amide of the present invention is derived from C ₁₈those of unsaturated fatty acids.

Aliphatic amide and diethoxy long-chain amine such as N, N-pair-(2-hydroxyethyl)-tallow amine itself are generally used as friction modifier component of the present invention.Two class amine are commercially available.Aliphatic amide and ethoxylated fatty amine are described in greater detail in United States Patent (USP) 4, and 741, in 848.

Friction improver can be present in the present composition with the content of at least 0.05,0.1,0.15,0.2,0.3,0.5 or even 1.0 % by weight.Friction improver can be less than 10,7.5,5, or even 4 or 3 % by weight to exist.

The present composition, especially friction modifier component optionally can comprise one or more other friction improvers.These other friction improvers can have or not have solvability and/or the compatibility problem of above-mentioned friction improver.These other friction improvers can comprise the ester of polyvalent alcohol, such as Rylo MG 19, and their berated derivatives; Fatty phosphites; Borated fatty epoxides; Olefine sulfide; Derived from the compound of hydroxycarboxylic acid as oil base tartrimide, stearyl tartrimide and tartrate 2-ethylhexyl; And composition thereof.

The ester of polyvalent alcohol comprises the fatty acid ester of glycerine.These can by multiple method preparation known in the art.These esters many are if Rylo MG 19 and glycerine one tallow acid esters are with commercial mass production.Be oil-soluble for ester of the present invention and preferably by the C such as found in natural product ₈-C ₂₂lipid acid or the preparation of its mixture.Lipid acid can be saturated or undersaturated.Some compound found in from the acid of natural origin can comprise the licanic acid containing a ketone groups.Useful C ₈-C ₂₂lipid acid is those of formula R-COOH, and wherein R is alkyl or alkenyl.

The fatty monoesters of glycerine is useful.The mixture of monoesters and diester can be used.The mixture of monoesters and diester can contain the monoesters at least about 40%.Can use containing the monoglyceride of 40 to about 60 % by weight monoesters and the mixture of diester of having an appointment.Such as, the business Rylo MG 19 of the mixture containing 45-55 % by weight monoesters and 55-45% diester can be used.

The useful lipid acid preparing these fatty acid esters comprises oleic acid, stearic acid, Unimac 5680, palmitinic acid, tetradecanoic acid, Zoomeric acid, linolic acid, lauric acid, linolenic acid and eleostearic acid, and from the acid of natural product: tallow, plam oil, sweet oil, peanut oil.

Friction improver derived from hydroxycarboxylic acid reacts by acid and alcohol and/or amine and is formed.Suitable hydroxycarboxylic acid comprise that formula II represents those:

formula II

Wherein: a and b can be the integer of 1-5 or 1-2 independently; X can be aliphatic series or alicyclic group, or containing the aliphatic series of Sauerstoffatom or alicyclic group in carbochain, or the above-mentioned type group replaced, and described group contains 6 carbon atoms and have a+b effectively tie point at the most; Each Y can Wei – O –, >NH or >NR independently ³, or two Y represent the imide structure R formed between two carbonyls together ¹the nitrogen of-N<; And each R ¹and R ³can be hydrogen or alkyl independently, condition be at least one R ¹and R ³group can be alkyl; Each R ²can be hydrogen, alkyl or acyl group independently, further condition be at least one-OR ²group is positioned at X relative at least one-C (O)-Y-R ¹group is on the carbon atom of α or β.

In one embodiment, acid is represented by formula III:

formula III

Wherein each R ⁴be H or alkyl independently, or wherein R ⁴group forms ring together.In one embodiment, friction improver is boration.In another embodiment, not by friction improver boration.

In officely how go up in embodiment, hydroxycarboxylic acid can be tartrate, citric acid or its combination, can also be the reactive equivalent (comprising ester, acyl halide or acid anhydride) of this kind of acid.Gained friction improver can comprise the imide of tartrate, citric acid or its mixture, diester, diamide or ester-acid amide derivative.In one embodiment, the derivative of hydroxycarboxylic acid comprises tartaric imide, diester, diamide or ester-acid amide derivative.

Amine used in the preparation of friction improver can have formula RR ' NH, and wherein each R and R ' represents H independently, has 1 or 8 to 30 or 150 carbon atom, i.e. the hydrocarbyl group of a 1-150 or 8-30 or 1-30 or 8-150 atom.Also the amine of the carbon atom range with lower limit 2,3,4,6,10 or 12 carbon atoms and the upper limit 120,80,48,24,20,18 or 16 carbon atoms can be used.In one embodiment, each radicals R and R ' have 8 or 6 to 30 or 12 carbon atoms.In one embodiment, in R and R ', carbon atom sum is at least 8.R and R ' can be linear or branching.In one embodiment, R and R ' is for linear and have at least 12 carbon.In this kind of embodiment, group can comprise that some are unsaturated.

Alcohol for the preparation of friction improver contains 1 or 8 to 30 or 150 carbon atom similarly.Also the alcohol of the carbon atom range with lower limit 2,3,4,6,10 or 12 carbon atoms and the upper limit 120,80,48,24,20,18 or 16 carbon atoms can be used.In certain embodiments, in the group that alcohol is derivative, carbonatoms can be 8-24,10-18,12-16, or 13 carbon atoms.

Alkohol and amine can be linear or branching, and if be branching, then side chain can appear at any point in chain and side chain can have any length.In some embodiments, alcohol used and/or amine comprise hyperbranched compounds, and in the other embodiments again, alkohol and amine used is at least 50%, 75% or even 80% branching.

In some embodiments, alcohol used and/or amine comprise branching C _6-18or C _8-18alcohol, branching C _12-16alcohol, 2-Ethylhexyl Alcohol, different tridecanol, linear C _6-18or C _8-18alcohol, linear C _12-16alcohol, or its combination.

In one embodiment, the compound that the friction improver that alcohol acid derives can represent for formula IV:

formula IV

Wherein n ' is 0-10; P is 1-5; Y and Y ' is-O-, >NH, >NR independently ⁷, or be connected by Y with Y ' group, thus R is formed between two >C=O groups ¹-N< group and the imide group formed; R ⁵and R ⁶be the alkyl usually containing 1,4 or 6 to 150,30 or 24 carbon atom independently; M is 0 or 1 and X is-CH independently ₂-, >CHR ⁸or >CR ⁸r ⁹, >CHOR ¹⁰, or >C (CO ₂r ¹⁰) ₂,-CH ₃,-CH ₂r ⁸or-CHR ⁸r ⁹,-CH ₂oR ¹⁰, or-CH (CO ₂r ¹⁰) ₂, or its mixture, wherein: R ⁷for alkyl; R ⁸and R ⁹be ketone group containing group (such as acyl group), ester group or alkyl independently; And R ¹⁰be hydrogen or the alkyl usually containing 1-150 carbon atom independently.

In some embodiments, the compound that formula IV represents has X (the such as >CHOR of at least one hydroxyl ¹⁰, wherein R ¹⁰for hydrogen).When X hydroxyl, compound can derived from hydroxycarboxylic acid, such as tartrate, citric acid or its mixture.In one embodiment, compound deriving is from citric acid and R ⁵and R ⁶containing at least 6 or 8 carbon atoms to 150, or 6 or 8 to 30 or 24 carbon atoms.In one embodiment, compound deriving is from tartrate and R ⁵and R ⁶containing 4 or 6 to 30 or 24 carbon atoms.When X not hydroxyl time, compound can derived from propanedioic acid, oxalic acid, chloro-phenyl-propanedioic acid, its reactive equivalent as ester, or its mixture.

In some embodiments, the present composition does not comprise these optional friction improvers any, and in other embodiments, one or more any optional friction improvers listed herein are not present in the present composition.

In other embodiments, there is other friction improver, and this friction improver is derived from alcohol acid.In other embodiments, other friction improver is oil base tartrimide, stearyl tartrimide, 2-ethylhexyl tartrimide or its combination.

Other friction improver can be present in the present composition with the content of at least 0.05,0.1,0.15,0.2,0.3,0.5 or even 1.0 % by weight.Other friction improver can be less than 10,7.5,5, or even 4 or 3 % by weight to exist.

stablize component

The present composition comprises stable component.The present invention stablizes components be soluble in medium and to improve with the friction improver solvability making it in medium and/or total composition that interacts.This combines with friction improver by stablizing component, produces and keeps the degree than larger by independent friction improver gained to suspend, disperse and/or be dissolved in the suspended particle of the associated molecule in medium and/or total composition and realize.

The present invention stablize component be in media as well with friction improver in conjunction with time cause the additive that the turbidity of composition improves compared with not comprising the same combination of stable component.

Stable component can comprise: (i) metal: matrix, than the high alkaline detergent being greater than 3:1, comprises its boration variant; (ii) alkyl imidazoline; (iii) amine salt of hydrocarbyl phosphate or acid esters, hydrocarbylthio phosphoric acid or acid esters, hydrocarbyl dithiophosphoric acid or acid esters, one or more these acid and acid esters, or its combination; (iv) alkylbenzene sulfonate or derivatives thereof; Or its combination.

high alkaline detergent.

Stable component can comprise high alkaline detergent.Suitable purification agent has the metal being greater than 3:1: matrix ratio.Overbased material, also referred to as high alkalinity or hyperalkaline salt, is generally single phase homogeneous Newtonian systems, it is characterized in that according to metal and with the stoichiometry of the concrete acidic organic compound of metal reaction in and the amount of required excess metal.The amount of excess metal represents with " matrix: metal than " usually, and it is the total yield of metal and the ratio of the equivalent of matrix.Being described in more detail in " Chemistry andTechnology of Lubricants " of term metal ratio, the 2nd edition, R.M.Mortier and S.T.Orszulik edits, and the 85th and 86 pages, provide in 1997.

The basicity of overbased material generally represents with total basicnumber (TBN).The amount of the acid (perchloric acid or hydrochloric acid) of TBN needed for the basicity of all overbased material of neutralization.The amount of acid is expressed as potassium hydroxide (mgKOH/g sample).Overbased material titration measures as indicator 0.1N hydrochloric acid soln by using tetrabromophenol sulfonphthalein by TBN.The equivalent of overbased material is determined by following equation: equivalent=(56,100/TBN).Overbased material of the present invention generally has at least 100 or 200 or 250 or 255, and be generally less than 450 or be not more than 400 total basicnumber.

High alkaline detergent is by acid material (usual mineral acid or low-grade carboxylic acid, such as carbonic acid gas) and comprise acidic organic compound, reaction medium, the metal base of stoichiometric excess and the mixture reaction of promotor and prepare, described reaction medium comprises the inert organic solvents (mineral oil, petroleum naphtha, toluene, dimethylbenzene etc.) of at least one for described acidic organic material.Useful acidic organic compound comprises carboxylic acid, sulfonic acid, phosphoric acid, phenol (comprising alkylated phenol) or its two or more mixture.In some embodiments, acidic organic compound is sulfonic acid or phenol.In whole specification sheets, unless otherwise expressly stated, any of acid mentions, such as carboxylic acid or sulfonic acid, is intended to comprise it and produces acid derivative, such as acid anhydride, lower alkyl esters, acyl halide, lactone and composition thereof.

Suitable high alkaline detergent comprises the high alkaline calcium sulfonate derived from sulfonic acid.Suitable acid comprises sulfonic acid and thiosulfonic acid, and salt, and comprises list or polynuclear aromatic or alicyclic compound.Oil-soluble sulfonic acid salt can be represented by a following formula mostly: R ₂-T-(SO ₃ ^-) _aand R ₃-(SO ₃ ^-) _b, wherein T is ring nucleus, such as benzene, toluene, naphthalene, anthracene, phenyl ether, diphenyl sulfide, oil naphthenic hydrocarbon or its combination; R ₂for aliphatic group is as alkyl, alkenyl, alkoxyl group, alkoxyalkyl or its combination; (R ₂)+T contains total at least 15 carbon atoms; And R ₃for the aliphatic hydrocarbyl containing at least 15 carbon atoms.R ₃can be alkyl, alkenyl, alkoxyalkyl or carbon alkoxyalkyl.In one embodiment, sulfonic acid has the substituting group (R derived from a kind of said polyolefins ₂or R ₃), in some embodiments, as mentioned above can derived from PIB.

By with such as SO ₃it is well known by persons skilled in the art that reaction and the by product produced by purification agent prepare sulfonate.For example, see John Wiley & Sons, N.Y. the article " Sulfonates " in (1969) Kirk-Othmer " Encyclopedia of Chemical Technology " of publishing, 2nd edition, the 19th volume, the 291st and page subsequently.

Metallic compound for the preparation of alkaline metal salt is generally any race 1 or race 2 metallic compound.In some embodiments, metal used is sodium or potassium, or even sodium.In other embodiments, the metal of metal base comprises race 2a alkaline-earth metal as magnesium, calcium and barium, and race's 2b metal is as zinc.In some embodiments, race 2 metal is magnesium, calcium, barium or zinc, is magnesium or calcium in some embodiments, or even calcium.Metallic compound can be used as metal-salt and provides.The anionicsite of salt can be hydroxide radical, oxygen, carbonate, borate and/or nitrate radical.

Acid material can be used for the formation realizing high alkaline detergent.Acid material can be that liquid is as formic acid, acetic acid, nitric acid and/or sulfuric acid.Acetic acid is useful especially.Also mineral acid material can be used as HCl, SO ₂, CO ₂and H ₂s.In some embodiments, material therefor is CO ₂, its usually and acetic acid combinations use.Sour gas can be used to realize the formation of high alkaline detergent, such as carbonic acid gas or sulfurous gas.

Promotor is for promoting that metal is incorporated to the chemical in basic metal composition.Especially comprehensively discussing at United States Patent (USP) 2 of Suitable accelerators, 777,874,2,695,910 and 2,616, find in 904.These comprise alcohols and phenol accelerant.Alcohols promotor comprises the alkanol with 1-12 carbon atom, such as methyl alcohol, ethanol, amylalcohol, octanol, Virahol, and these mixture etc.Phenol accelerant comprises benzene and the naphthalene of the replacement of multiple hydroxyl.Sometimes the mixture of various promotor is used.

High alkalinity salt also can be boration title complex.This kind of boration title complex by preparing the heating of an alkali metal salt boric acid at about 50-100 DEG C, and the equivalents of boric acid equals the equivalents of metal in salt roughly.U.S. Patent No. 3,929,650 disclose this boration title complex and their preparation method.

Suitable high alkaline detergent also comprises derived from those of phenol and alkylated phenol, and it can be described as phenates, such as sulfuration calcium phenylate.Phenates can be sulfur-bearing phenates, methylene-bridged phenates or its mixture.In one embodiment, phenates is sulfur-bearing/coupling phenates.This kind of material is described in U.S. Patent No. 6,551,965 and EP open EP 1903093A, EP 0601721A, in EP 0271262B2 and EP 0273588B2.

Suitable phenate detergents can be formed by alkylphenol, alkaline earth metal alkali and reaction of Salmon-Saxl, and it carries out forming metal sulphide phenates usually under the existence of promotor solvent.For the alkylphenol in the present invention, there is formula R (C ₆h ₄) OH, wherein R is the straight or branched alkyl with 8-40 or 10-30 carbon, and structure division (C ₆h ₄) be phenyl ring.The example of appropriate alkyl comprises octyl group, decyl, dodecyl, tetradecyl and hexadecyl.

Alkaline earth metal alkali can be any above-mentioned those, be calcium and/or magnesium in some embodiments.Example comprises calcium oxide, calcium hydroxide, barium oxide, hydrated barta, magnesium oxide etc.Calcium hydroxide, also referred to as white lime, is the most frequently used.Promotor solvent, also referred to as mutual solvent, can for having any stable organic liquid of proper solubility to alkaline earth metal alkali, alkylphenol and metal sulphide phenates intermediate.Suitable solvent comprises glycol and glycol monoethers as ethylene glycol, BDO, and the derivative of ethylene glycol, such as monomethyl ether, an ether etc.In one embodiment, solvent is one or more vicinal diol, and in another embodiment, solvent comprises ethylene glycol.Sulphur used in reaction can be the elementary sulfur of molten sulfur form.

In some embodiments, phenate detergents is prepared under the existence of cosurfactant.The acylating agent that suitable cosurfactant comprises low alkali alkylbenzene sulfonate, alkyl replaces is as polyisobutenyl succinic anhydride (PIBSA), and succinimide dispersants is as polyisobutenyl succinimide.Suitable sulfonate comprises the sulfonate that molecular weight is preferably greater than 400, and it will be by will be C derived from chain length ₁₅-C ₈₀alkene or C ₂-C ₄the alkylbenzene of the polymkeric substance of alkene and alkaline-earth metal obtain as sulfonation such as calcium, barium, magnesium.Suitable cosurfactant comprises and/or can derived from PIBSA, and described PIBSA itself can derived from 300-5000, or 500-3000, or 800-1600 number-average molecular weight polyisobutene.

As mentioned above, these phenate detergents, by making they and carbon dioxide under the existence of other alkaline earth metal alkali, react and high alkalization usually under the existence of promotor solvent.In one embodiment, the sulfuration phenate detergents of composition can be represented by lower formula V:

formula V

Wherein number of sulfur atoms y can be 1 to 8,6 or 4; R ⁵can be hydrogen or alkyl; T be hydrogen or in hydrogen, ion or non-phenols alkyl (S) of end-blocking _ykey; W can be the integer of 0-4; And M is hydrogen, valent metal ion, ammonium ion and composition thereof.

When M is equivalents of metal ion, metal can be the mixture of monovalence, divalence, trivalent or this metalloid.When for monovalence, metal M can be that basic metal is as lithium, sodium, potassium or its combination.When for divalence, metal M can be the mixture of alkaline-earth metal as magnesium, calcium, barium or this metalloid.When for trivalent, metal M can be aluminium.In one embodiment, metal is alkaline-earth metal, and in another embodiment, metal is calcium.

Above monomeric unit combines the oligopolymer to form hydrocarbylphenol for x time with self by this way.When x equals 0,1,2,3 and 4, oligopolymer is described as dipolymer, trimer, tetramer, pentamer and sexamer.Usually, the number of oligopolymer that x represents can be 0,1 to 10,9,8,6,5 or even 2.If concentration is 0.1,1 or even more than 2 % by weight, then oligopolymer exists with significant quantity usually.If concentration is for being less than 0.1 % by weight, then oligopolymer exists with trace usually.Generally speaking, for the molecule of at least 50%, x is 2 or higher.In some embodiments, total sulfur-bearing phenate detergents contains and is less than 20 % by weight dimeric structures.

In above structure, each R ⁵can be hydrogen or containing 4,6,8 or 9 to 80,45,30 or 20 carbon atoms, or the alkyl of 14 carbon atoms.Each aromatic ring is different from the R of hydrogen ⁵substituent number (w) can be 0 or 1 to 4,3 or 2, or is just 1.If there is two or more alkyl, then they can be identical or different, and for guaranteeing oil soluble, the minimum the total number of carbon atoms existed in the hydrocarbyl substituent on all rings can be 8 or 9.Preferred component comprises containing having 9-14,4-alkylated phenol of the alkyl of the carbonatoms of such as 9,10,11,12,13,14 and composition thereof.4-alkylated phenol contains sulphur usually on 2.The phenate detergents of above representation also can use alkaline earth metal alkali as the alkalization of calcium hydroxide height.

In some embodiments, be high alkaline sulfurating earth metal alkyl phenates for the phenate detergents in the present invention, it can have formula R-CH (R optionally through being incorporated at least one ¹) carboxylic acid of-COOH or its acid anhydride or ester and be modified, wherein R is C ₁₀-C ₂₄straight chained alkyl, and R ¹for hydrogen.This kind of high alkalinity phenates is prepared by following component reaction: (i) non-high alkalinity Sodium Sulphide earth metals alkyl phenates described above, (ii) alkaline earth metal alkali that can be used as entirety or add with increment, (iii) has polyvalent alcohol, two-or the three-(C of 2-4 carbon atom ₂-C ₄) glycol, aklylene glycol alkyl oxide or alkyl ether, (iv) as the lubricating oil that thinner exists, v carbonic acid gas that () adds at every turn after adding component (ii), and optional (vi) at least one carboxylic acid as defined above.

Component (ii) can be any above-mentioned earth metals alkali, is calcium hydroxide in some embodiments.

Component (iii) may suitably be dibasic alcohol as ethylene glycol or propylene glycol, or trivalent alcohol is as glycerine.Two-or three-(C ₂-C ₄) glycol may suitably be glycol ether or triglycol.Aklylene glycol alkyl oxide or alkyl ether can have following formula suitably: R (OR ¹) _xoR ², wherein R is C ₁-C ₆alkyl, R ¹for alkylidene group, R ²for hydrogen or C ₁-C ₆alkyl, and x is the integer of 1-6.Suitable example comprises monomethyl or the dimethyl ether of ethylene glycol, glycol ether, triglycol or Tetraglycol 99.Specially suitable solvent is diethylene glycol monomethyl ether.Also the mixture of glycol and glycol ethers can be used.In some embodiments, glycol or glycol ethers and inorganic halides combinationally use.In one embodiment, component (c) is ethylene glycol or diethylene glycol monomethyl ether, and the latter and ammonium chloride and acetic acid combinations use.

In some embodiments, component (vi) is for having R group by the carboxylic acid of phenates modification, and described R group is the unbranched alkyl radical that can contain 10-24 or 18-24 carbon atom.The example of suitable saturated carboxylic acid comprises capric acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid, mountain acid and lignoceric acid.Also the mixture of acid can be used.Replace, or except carboxylic acid, acid anhydrides or the ester derivative of acid can be used, preferred anhydrides.In one embodiment, acid used is stearic acid.

In some embodiments, the sulphur except already present via component (i) can be added in reaction.Above-mentioned reaction can be carried out in the presence of a catalyst.Suitable catalyzer comprises hydrogenchloride, calcium chloride, ammonium chloride, aluminum chloride and zinc chloride.

In one embodiment, high alkaline detergent of the present invention be following any one or more: derived from the high alkaline detergent of alkylated phenol, itself is derived from conventional PIB; Derived from the calcium sulphonate high alkaline detergent of sulfonic acid, itself is derived from conventional PIB, and its boration variant optional.In some embodiments, purification agent has the TBN of at least 200,255 or 290.In other embodiments, calcium sulphonate of the present invention has the TBN of at least 270 or 280.In this kind of embodiment, the TBN of high alkaline detergent can be less than 500,450 or be not even greater than 400.

In some embodiments, the present invention stablizes high alkaline detergent used in component and can comprise the above-mentioned overbased sulfonate that one or more TBN are at least 200 or 280.Purification agent also can comprise the above-mentioned high alkalinity phenate detergents that any one TBN is at least 30,50,120 or at least 200 or 250.

alkyl imidazoline

In some embodiments, stable component comprises alkyl imidazoline.This kind of material can derived from carboxylic acid and amine, comprises the reaction of alkylene polyamine.

In some embodiments, alkyl imidazoline also comprises the succinic acylating agent of alkyl replacement and the reaction product of polyamines.This kind of material is described in U.S. Patent No. 4, and 234, in 435.But in some embodiments, alkyl imidazoline of the present invention does not comprise the additive of the succinic acylating agent replaced derived from alkyl.

In other embodiments, alkyl imidazoline be aliphatic group monocarboxylic acylating agent as lipid acid, with the condensation product of polyamines.

The hydrocarbyl portion of aliphatic group monocarboxylic acylating agent can be aliphatic group.Aliphatic group can be linear, branching, or its mixture.Aliphatic group can be saturated, undersaturated, or its mixture.Aliphatic group can have 1-50 carbon atom, in another case 2-30 carbon atom, in another case 4-22 carbon atom, and preferably 8,10 or 12 to 20 carbon atoms.If aliphatic group monocarboxylic acylating agent is aliphatic carboxylic acid, then it can be considered and comprises carboxyl (COOH) and aliphatic group.Therefore, the total number of carbon atoms in carboxylic acid can be 2,3,5,9 or 13 to 51,31,23,11 or 21.Monocarboxylic acylating agent can be monocarboxylic acid or its reactive equivalent, such as acid anhydride, ester, or acyl halide is as stearyl chloride.Useful monocarboxylic acylating agent is commercial by a large amount of manufacturer, and comprises ready denier oil acid, oleic acid, stearic acid and Unimac 5680.In some embodiments, lipid acid contains 12-24 carbon atom, in some embodiments 18 carbon atoms, such as stearic acid, Unimac 5680 and combination thereof.

Polyamines is the amine with two or more amine groups, wherein the first amine groups be primary amine group and the second amine groups be uncle or secondary amine group.The reaction product of carboxylic acid and polyamines can containing depending on that the heterocyclic reaction products useful of the larger or less amount of reaction conditions is as 2-tetrahydroglyoxaline reaction product and amide condensed product.Polyamines can have 2-30 carbon atom, in some embodiments, comprises Alkylenediamine, N-alkylenediamines and polyalkylenepolyamines.Useful polyamines comprises quadrol, 1，2-diaminopropane, N-methyl-quadrol, N-tallow base (C ₁₆-C ₁₈)-1,3-propylene diamine, N-oil base-1,3-propylene diamine, polyethylene polyamine is as diethylenetriamine and Triethylenetetramine (TETA) and tetren and polyethylene polyamine bottoms.

In another embodiment of the present invention, monocarboxylic acylating agent and polyamines are respectively C ₄-C ₂₂aliphatic carboxylic acid and Alkylenediamine or polyalkylenepolyamines, in another embodiment, aliphatic carboxylic acid is Unimac 5680 and polyamines is that polyethylene polyamine is as tetren.

phosphor-included additive

Stable component also can comprise phosphor-included additive, such as hydrocarbyl phosphite, thiophosphoric acid hydrocarbyl carbonate or phosphorodithioic acid dialkyl ester or its combination, and the amine salt of one or more this kind of materials.This kind of additive generally passes through one or more phosphorous acid as phosphoric acid or thiophosphoric acid, comprises phosphorodithioic acid, reacts and prepare, and comprise the full ester of phosphoric acid or thiophosphoric acid or the amine salt of partial ester with unsaturated amides as acrylamide.

Be applicable to prepare phosphoric acid that the present invention stablizes component and comprise the phosphorous acid ester reacting by one or more phosphorous acid or acid anhydride and alcohol and prepare.Alcohol used can containing at the most about 30,24,12 or even 3 carbon atoms.Phosphorous acid or acid anhydride can be inorganic phosphorus reagent, such as Vanadium Pentoxide in FLAKES, phosphorus trioxide, phosphorus tetroxide, phosphorous acid, Phosphorates phosphorus Halides, rudimentary phosphide, or phosphoric sulfide, comprise thiophosphoric anhydride.In some embodiments, phosphorous acid is Vanadium Pentoxide in FLAKES, thiophosphoric anhydride, phosphorus trichloride or its combination.Phosphorous acid ester can be the monoesters of phosphoric acid or diester or its mixture.

The example of commercially available alcohol comprises Alfol 810 (having the mixture of the main straight chain primary alcohol of 8-10 carbon atom); Alfol 1218 (mixture of the synthesis straight chain primary alcohol containing 12-18 carbon atom); Alfol 20+ alcohol (mainly has C ₂₀c ₁₈-C ₂₈the mixture of primary alconol); With Alfol 22+ alcohol (mainly containing C ₂₂the C of alcohol ₁₈-C ₂₈primary alconol).

In another embodiment, phosphoric acid is thiophosphite, and can be list-or dithio phosphorous acid ester.Thiophosphite is also referred to as thiophosphoric acid.Thiophosphite by phosphoric sulfide as above-mentioned those and any above-mentioned alcohol react and prepare.Single thiophosphate ester or single thiophosphate ester react by sulphur source such as elementary sulfur and phosphorous acid dialkyl ester and prepare.Sulphur source also can be organic sulfide, such as sulphur coupling alkene or phosphorodithioate.Single thiophosphate ester is also by adding phosphorous acid dialkyl ester containing sulphur source as formed in lubricant mixture in the lubricating composition of olefine sulfide.

Phosphorodithioic acid or phosphorodithioic acid can react with epoxide or glycol, and react with phosphorous acid, acid anhydride or lower member ester further.Epoxide can be aliphatic epoxide or Styrene oxide 98min., such as ethylene oxide, propylene oxide, oxybutylene, octylene oxide, oxidation laurylene and Styrene oxide 98min..In one embodiment, propylene oxide is used.Glycol can for having the aliphatic diol of 1 or 2 to 12,6 or 3 carbon atoms.This material can with P ₂o ₅reaction, then uses amine salt.

Above-mentioned acid phosphoric acid ester can react to form ammonium salt with ammonia or amine compound.This salt can be individually formed, and then the salt of phosphorous acid ester can be added in lubricating composition.As selection, salt also original position can be formed when acidic phosphite and other component being mixed to form the lubricating composition prepared completely.

Suitable amine comprises monoamine and polyamines, comprise above-mentioned those.Amine can be primary amine, secondary amine or tertiary amine.Useful monoamine can contain 1 to 24,14 or 8 carbon atom, comprises methylamine, ethamine, propylamine, butylamine, octylame and amino dodecane, dimethylamine, diethylamine, dipropyl amine, dibutylamine, methylbutylamine, ethylhexylamine, Trimethylamine 99, Tributylamine, methyl-diethyl-amine, ethyl dibutylamine etc.

In one embodiment, amine can be fat (C _4-30) amine, include but not limited to normal hexyl Amine, n-octyl amine, n-Decylamine, n-dodecylamine, positive tetradecy lamine, hexadecylamine, octadecyl amine, oleyl amine etc.Some examples are that commercially available aliphatic amide such as " Armeen " amine (can by Armak Chemicals, Chicago, the product that Illinois obtains), Armeen-C, Armeen-O, Armeen-OL, Armeen-T, Armeen-HT, Armeen S and Armeen SD of such as Armak, wherein the alphabetical trade mark relates to fat group, such as cocounut oil, oil base, tallow or soybean group.

The C that useful amine provides with trade(brand)name Primene 81R for Rohm and Haas _12-14branching primary t-alkyl-amine.In one embodiment, stable component is the amine salt of the amine salt of the mixture of phosphoric acid and ester and/or the mixture of phosphorodithioic acid and ester, wherein by the mixture salinization of mixture Primene 81R or similar amine or amine.

These phosphor-included additives, the preparation comprising the amine salt of above-mentioned acid and ester discusses in more detail in U.S. Patent No. 6617287.

In one embodiment, phosphor-included additive of the present invention be following one or more: phosphoric acid, as hydrocarbyl phosphite, thiophosphoric acid hydrocarbyl carbonate, phosphorodithioic acid hydrocarbyl carbonate and combination thereof, comprises the mixture of its dialkyl variant; The amine salt of the mixture of this kind of phosphoric acid and/or its full ester or partial ester; (iii) amine salt of the mixture of this kind of phosphorodithioic acid and/or full ester or partial ester.

alkylbenzene sulfonate

The above-mentioned sulfonic acid itself being applicable to prepare high alkaline detergent also can be used as stablizer.In one embodiment, stablizer comprises sulfonic acid and thiosulfonic acid and salt thereof, and comprises list or polynuclear aromatic or alicyclic compound.This kind of sulfonate is generally oil-soluble, and is represented by a following formula in some embodiments: R ₂-T-(SO ₃ ^-) _aand R ₃-(SO ₃ ^-) _b, wherein T is ring nucleus, such as benzene, toluene, naphthalene, anthracene, phenyl ether, diphenyl sulfide, oil naphthenic hydrocarbon or its combination; R ₂for aliphatic group is as alkyl, alkenyl, alkoxyl group, alkoxyalkyl or its combination; (R ₂)+T contains total at least 15 carbon atoms; And R ₃for the aliphatic hydrocarbyl containing at least 15 carbon atoms.R ₃can be alkyl, alkenyl, alkoxyalkyl or carbon alkoxyalkyl.In one embodiment, sulfonic acid has the substituting group (R derived from a kind of said polyolefins ₂or R ₃), in some embodiments, as mentioned above can derived from PIB.In one embodiment, stablizer of the present invention comprises alkylbenzene sulfonate, and wherein alkyl derivative is from PIB.

In some embodiments, stabilizer package of the present invention is containing the compound that can be represented by formula VI:

formula VI

Wherein: X ¹for Sauerstoffatom, sulphur atom, alkylene Huo – NR ²; X ²for Sauerstoffatom or sulphur atom; X ³for=P (OR ²) < or=S (O) <; Y Wei – R ²huo – OR ²; Each R ¹for alkylene; Each R ²be alkyl Huo – H independently; And each n is 0 or 1 independently.In some embodiments, the present invention stablizes the salinization variant that component comprises one or more above-claimed cpds.In any above-mentioned embodiment, the X of formula VI ²also can be alkyl, and X ³can be=C<, wherein X ²alkyl by such as formula shown in double bond or singly-bound be connected to X ³carbon atom on.In other embodiments again, the X of formula VI ²think alkyl, and X ³can be=C<, wherein about [R ¹] n of group is 0.Various stable component, comprise many above-mentioned those belong to this formula and/or at least one its described in embodiment.

In some embodiments, stable component comprises two anchor points and dissolves the compound of element.Anchor point can be electron donor(ED) as H key acceptor, and/or electron acceptor(EA) is if H key is to body.In some embodiments, two anchor points are extremely close each other in the molecule of the compound of stable component.Such as, anchor point can in 10 each other, 8,6 or even in 4 carbon atoms.In some embodiments, anchor point in the carbon atom of 2 each other, or is even connected on adjacent carbons.Dissolve element and can be enough to for length the alkyl that compound some solvability levels are in media as well provided.Dissolving element also can be micella, and compound connects thereon, therefore keeps it in media as well.Many aforementioned stable components meet these requirements, as meet the various acid amides of above formula VI and acid compound accomplished.

industrial application

The present invention includes the method preparing composition, it comprises and following component being combined: (a) comprises the medium of solvent, functional liquid or its combination; B () is not exclusively dissolved in the friction modifier component in medium; (c) to dissolve in (a) and to interact the stable component that the solvability that makes (b) in (a) improves with (b).The inventive method relates to and component (b) and (c) to be added in component (a) and make the particle of component (b) and (c) have the mean diameter being less than 10 μm component mixing.The inventive method produces limpid and/or stable mixture, namely friction improver can not spill from solution, mixture can not be made to show muddiness or preformed casse, keep suspending, disperseing and/or be dissolved in mixture, or its combination, or at least demonstrate improvement one or more in these aspects when compared with not comprising the same combination of stable component.

Although be reluctant bound by theory, think at least some embodiment, the present composition improves stability and/or the consistency of friction modifier component in total composition, because friction modifier component solubilizing agent is dissolved in title complex.

In some embodiments, the inventive method produces the mixture with the transparency of improvement compared with not comprising the same combination of stable component, as defined by lower JTU and/or NTU value.

As mentioned above, the form that component (b) and (c) can be less than the discrete particles of 10 μm with mean diameter is present in component (a).In some embodiments, particle has the mean diameter being less than 10,5 or 3 μm.In other embodiments, particle has the mean diameter of 0.01,0.02,0.03 or 0.09 to 10,6,5 or 3 μm.In some embodiments, the particle of 80% meets one or more above-mentioned limitation of size.In other embodiments, the particle of 90%, 95%, 99% or even 100% meets limitation of size.The method forming particle is exceeded limited, can comprise and use conventional equipment and/or technology by component (a), (b) and (c) mixing.

In some embodiments, the present composition and/or the composition that produced by the inventive method comprise final functional liquid and multifunctional additive for lubricating oils.Final functional liquid is fluid namely.Multifunctional additive for lubricating oils for containing all additives needed for final fluid, but be the composition of conc forms.This make transport and process easier.At the appropriate time can by multifunctional additive for lubricating oils and fluid, solvent, or similar thinner, and the mixing of other additive is to produce final functional liquid namely.

When referring to final functional liquid, composition involved in the present invention can comprise: 1, component (a) medium of 3 or 10 to 99,80 or 70 % by weight; 0.1, component (b) friction improver of 0.2,0.3,0.5 or 1.0 to 10,7.5,5,4 or 3 % by weight; Component is stablized with the component (c) of 0.1,0.2,0.3,0.5 or 2.0 to 20,10,8,5,4 or 2 % by weight.

When referring to multifunctional additive for lubricating oils, composition involved in the present invention can comprise: component (a) medium of 0.1,1,3 or 10 to 90,60,50,30, or 20 % by weight; 0.1, component (b) friction improver of 0.5,1,5 or 8 to 60,30,20 or 10 % by weight; Component is stablized with the component (c) of 0.1,0.2,0.3,0.5 or 2.0 to 20,10,8,5,4 or 2 % by weight.As mentioned above, in some embodiments, medium and stable component can be same material, and in this case, bifunctional material can exist with any scope provided about component (a) or (c) above.

In some embodiments, the present composition makes component (b) form small-particle in component (a) and component (c) is formed for stablizing these particles by component (b) and (c) being mixed in component (a).In some embodiments, component (c) and component (b) form composite grain in component (a).In some embodiments, the particle of some or all of formation is in above-mentioned size.In other embodiments, those are larger than above-mentioned for some or even all particles.

In some embodiments, instant component is mixed by ordinary method.Required combined amount changes along with composition, and is enough to produce the particle with desired size and/or stability.In some embodiments, mix and realize by abrasive component, in other embodiments again, mix and realize by abrasive component at low temperatures.

In a this embodiment, can by friction improver in stable component, such as succinimide dispersants is as being mixed in oil under the existence of polyisobutenyl succinimide.Mixing can for using the form of the Ginding process of conventional grinding machine and technology.But in some embodiments, grinding at low temperatures, is being less than at 30 DEG C in some embodiments, in other embodiments, is completing at-10,0 or 5 to 30,25 or 20 DEG C.Cryogrinding by cold grinding equipment, pre-cooled component, during grinding by refrigerant as dry ice (solidified carbon dioxide) adds in component, or its combination realize.Resulting composition can be described as stabilising dispersions in some embodiments, in other embodiments, can be described as solubilize solution, or even its combination, the size of the particle that the key distinction wherein between this kind of embodiment may relate to.

In other embodiments, the present composition is not formed by grinding or other high-energy input method any, but is formed with simple mixing and considerably less energy input.

In some embodiments, the functional liquid used together with the present composition is fuel.Fuel composition of the present invention comprises aforementioned stable composition and liquid fuel, and for oil engine or open flame burner refuel.These compositions also can contain one or more other additives described herein.In some embodiments, the fuel be applicable in the present invention comprises any commercial fuel, in some embodiments any market available diesel oil fuel and/or biofuel.

Relate to according to the description of the fuel type be applicable in the present invention and can be present in the present invention containing the fuel in compositions of additives and the fuel that can add wherein containing compositions of additives and/or fuel additive concentrate composition.

The fuel be applicable in the present invention is exceeded limited.Generally speaking, suitable fuel, usually in envrionment conditions, such as, is liquid under room temperature (20-30 DEG C) or is usually liquid in the operating condition.Fuel can be hydrocarbon fuel, nonhydrocarbon fuel or its mixture.

Hydrocarbon fuel can be petroleum fractions, comprise as by ASTM specification D4814 the gasoline that defines, or the diesel oil fuel as defined by ASTM specification D975.In one embodiment, liquid fuel is gasoline, and in another embodiment, liquid fuel is white gasoline.In another embodiment, liquid fuel is diesel oil fuel.The hydrocarbon that hydrocarbon fuel can be prepared for natural gas synthetic oil method, comprises such as by hydrocarbon that method is prepared as Fischer-Tropsch method.In some embodiments, for the fuel in the present invention be diesel oil fuel, biodiesel fuel or its combination.

Suitable fuel also comprises comparatively heavy fuel oil, and such as No. 5 and No. 6 oil fuel, it is also referred to as residual fuel oil, heavy fuel oil (HFO) and/or boiler oil.This class A fuel A can be used alone or and other, usually compared with light fuel mixing with formed there is more low viscous mixture.Also comprise bunker fuel, it is generally used in ship engine.The fuel of these types has high viscosity and at ambient conditions can for solid, but when heating be liquid when feeding in the engine of its refuel or burner.

Nonhydrocarbon fuel for containing oxygen composition, can be commonly referred to oxygenate, and it comprises alcohol, ether, ketone, the ester of carboxylic acid, itroparaffin or its mixture.Nonhydrocarbon fuel can comprise methyl alcohol, ethanol, methyl tertiary butyl ether, methylethylketone, from the ester-exchanged oil of plant and animal and/or fat as coleseed methyl ester and soybean methyl ester, and Nitromethane 99Min..

The mixture of hydrocarbon and nonhydrocarbon fuel can comprise such as gasoline and methyl alcohol and/or ethanol, diesel oil fuel and ethanol, and diesel oil fuel and transesterify vegetables oil are as coleseed methyl ester and other biologically-derived fuel.In one embodiment, liquid fuel is the emulsion of water in hydrocarbon fuel, nonhydrocarbon fuel or its mixture.

In several embodiments of the present invention, liquid fuel can have based on weight 50,000ppm or less, 5000ppm or less, 1000ppm or less, 350ppm or less, 100ppm or less, 50ppm or less, or 15ppm or less sulphur content.

Liquid fuel of the present invention is present in fuel composition with the primary amount being generally greater than 95 % by weight, in other embodiments, to be greater than 97 % by weight, to be greater than 99.5 % by weight, to be greater than 99.9 % by weight, or is greater than 99.99 % by weight existence.

Above-mentioned composition also can comprise one or more other additives.This kind of additive comprises oxidation retarder and antioxidant, friction improver anti-wear agent, corrosion inhibitor or viscosity modifier, and be different from above-mentioned those dispersion agent and purification agent.These other additives may reside in medium, like this especially when medium comprises functional liquid.When it is present, 0,0.1,0.5 or 1 to 2,5,10 or 15% of total composition when these other additives consider final fluid, can be accounted for, when considering multifunctional additive for lubricating oils, account for 0,0.5,1 or 2 to 4,10,20 or 40 of total composition.

As above scope allowed, in one embodiment, multifunctional additive for lubricating oils can comprise additive of the present invention and substantially not containing other solvent any.In these embodiments, the multifunctional additive for lubricating oils containing additive of the present invention is pure, namely it does not comprise add to improve enriched material material processing feature as other solvent any of its viscosity.

As used herein, term alkyl and/or alkylene substituting group and/or group use with its conventional meaning well known to those skilled in the art.Specifically, it refers to have the carbon atom that is connected directly between on molecule rest part and mainly has the group of hydrocarbon character.Example comprises: hydrocarbon substituent, i.e. aliphatic series (such as alkyl or alkenyl), alicyclic (such as cycloalkyl, cycloalkenyl group) substituting group, with aromatics-, aliphatic series-and the aromatic substituent of alicyclic replacement, and wherein ring completes the cyclic substituents of (such as two substituting groups form ring together) by another part of this molecule; The hydrocarbon substituent replaced, namely contains the substituting group of the non-hydrocarbon (such as halogen (especially chlorine and fluorine), hydroxyl, alkoxyl group, sulfydryl, alkyl thiol, nitro, nitroso-group and sulfinyl) not changing substituent main hydrocarbon character in the context of the present invention; Assorted substituting group, namely in the context of the present invention, while there is main hydrocarbon character in the ring be made up of carbon atom or chain containing the substituting group being different from carbon.Heteroatoms comprises sulphur, oxygen, nitrogen, and comprises substituting group as pyridyl, furyl, thienyl and imidazolyl.Generally speaking, for every 10 carbon atoms, in alkyl, have no more than 2, preferably no more than 1 substituents; Usually, there is not substituents in alkyl.

More known above-mentioned materialss may interact in final preparaton, make the component of final preparaton may be different from those originally adding.Such as, metal ion (such as purification agent) can migrate to other acid or anionic site of other molecule.In addition, acylating agent and/or the present invention replace hydrocarbon additive with using and can to form salt or other title complex and/or derivative during their other component interaction of composition.The product formed thus, comprises the product formed through using the present composition with its intended use and may be not easy to describe.But all this kind of improvement and reaction product include within the scope of the invention; The present invention includes by the composition of preparation by said components mixing.

Unless otherwise noted, all percent value and ppm value are % by weight value and/or based on Weight computation herein.

Embodiment

The present invention is set forth further by following examples, and it sets forth particularly advantageous embodiment.Although provide this embodiment to set forth the present invention, they are not intended to limit it.

embodiment group 1.

By adding in lubricating composition prepare one group of sample by having the known stable component with the various levels of the friction improver of compatibility problem.The stable component of described increasing amount, by being added by the friction improver of described amount in one group of lubricating composition sample, then adds in each sample and prepares by sample.After adding, mixture be heated to 100 DEG C and stir until limpid.Then each sample cooling is also at room temperature stored.Then after storing 1 hour, 1 day, 3 days and 1 week time check that each sample is to check muddiness, preformed casse and even the spilling of friction improver.The amount (minimum of the stable component needed for lubricating composition limpid after being namely provided in storage one week) of the stable component needed for friction modifier component of one group of amount in lubricating composition stablized in record.Then this step is repeated with another friction modifier component concentration level.

Lubricating composition used in this sample group is the 0W20 GF-5 engine oil composition prepared completely.When existence 0 % by weight friction modifier component, said composition is limpid.Friction improver used in these samples is contained amide functional group and is formed by carboxylic acid and ammonia or amine reaction.Stable component used in these samples comprises: 300TBN calcium sulphonate high alkaline detergent (embodiment of the present invention 1-1); Derived from the alkyl benzene sulphonate (ABS) (embodiment of the present invention 1-2) of PIB; The amine salt (embodiment of the present invention 1-3) of the mixture of phosphoric acid and/or phosphorodithioic acid and ester; Derived from the alkyl imidazoline (embodiment of the present invention 1-4) of aliphatic mono-carboxylic acids and polyamines; Boration 300TBN calcium sulphonate high alkaline detergent (embodiment of the present invention 1-5); Derived from the non-boration polyisobutenyl succinimide dispersion agent of polyisobutenyl succinic anhydride and polyamines, wherein polyisobutenyl succinic anhydride is derived from PIB (comparative example 1-6).

Following table summarizes the result of embodiment group.

the result of table 1-embodiment group 1

Result shows the present invention and stablizes the composition that component generation has good stability.In addition, result shows the present invention and stablizes ratio of component and perform better surprisingly, as the embodiment of the present invention needs much lower processing rate to provide stabilized mixture compared with comparative example derived from derived from the polyisobutenyl succinic anhydride of PIB and the non-boration polyisobutenyl succinimide dispersion agent of polyamines.

Above referenced each file is incorporated to the present invention by reference.Except in embodiment, or outside clearly stating in addition, all quantity describing the amount of material, reaction conditions, molecular weight, carbonatoms etc. are in this manual to be understood that is modified by wording " about ".

Except as otherwise noted, each chemical mentioned herein or composition should be understood to the commercial grade material that can contain isomer, by product, derivative and usually be to be understood that other this kind of material be present in commercial grade.But except as otherwise noted, the amount of each chemical composition is expressed as to eliminate and usually can be present in any solvent in commercial materials or thinner.Be to be understood that the upper and lower bound of amount described herein, scope and ratio can combine independently.Similarly, the scope of each element of the present invention can use with the scope of other element any or together with measuring with amount.As used herein, the material comprising and do not affect in fact the fundamental sum new feature of composition considered is allowed in statement " substantially by ... composition ".

Claims

1. a composition, it comprises:

A () comprises solvent, functional liquid or its medium combined, wherein functional liquid is selected from gear oil, gear compound, hydraulic fluid, engine oil, two-stroke cycle oil, metal working fluids and fuel; With

B () is not exclusively dissolved in the friction modifier component in medium; With

C () to dissolve in (a) and to interact the stable component that the solvability that makes (b) in (a) improves with (b); The form that wherein component (b) and (c) are less than the discrete particles of 10 μm with mean diameter is present in component (a);

Wherein (b) friction modifier component comprises the compound that following formula represents:

Wherein X ⁴for Sauerstoffatom or sulphur atom; And each R ²and R ³be hydrogen or alkyl independently; With

Wherein component (c) is stablized component and is comprised: the amine salt of (i) hydrocarbyl phosphate or acid esters, hydrocarbylthio phosphoric acid or acid esters, hydrocarbyl dithiophosphoric acid or acid esters, one or more these acid and acid esters, or its combination; (ii) alkylbenzene sulfonate; Or its combination; With

Wherein in total composition, the concentration of component (b) is at least 0.1 % by weight.

2. composition according to claim 1, wherein turbidity improvement with do not stablize the same combination of component containing (c) compared with of total composition, defined by lower JTU and/or NTU value.

3. composition as claimed in one of claims 1-2, wherein friction improver comprises the compound derived from hydroxycarboxylic acid further.

4. composition as claimed in one of claims 1-2, wherein friction improver comprises oil base tartrimide, stearyl tartrimide, tartrate 2-ethylhexyl or its combination further.

5. prepare a limpid and method for stable composition, described composition comprises:

C () to dissolve in (a) and to interact the stable component that the solvability that makes (b) in (a) improves with (b);

Wherein X ⁴for Sauerstoffatom or sulphur atom; And each R ²and R ³be hydrogen or alkyl independently;

Wherein in total composition, the concentration of component (b) is at least 0.1 % by weight;

Described method comprises the steps:

I. component (b) and (c) are added in component (a);

II. the particle of component (b) and (c) is made to have the mean diameter being less than 10 μm described component mixing.

6. method according to claim 5, wherein transparency improvement with do not stablize the same combination of component containing (c) compared with of gained mixture, defined by lower JTU and/or NTU value.